CN110016203B

CN110016203B - Resin composition

Info

Publication number: CN110016203B
Application number: CN201811622499.4A
Authority: CN
Inventors: 川合贤司
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2018-01-09
Filing date: 2018-12-28
Publication date: 2023-10-31
Anticipated expiration: 2038-12-28
Also published as: JP2019119819A; TW201936771A; CN110016203A; TWI811275B; KR20190084890A; JP2022003125A; JP7296191B2; JP7272392B2

Abstract

The subject of the invention is to provide: a resin composition which can give a cured product having a low dielectric loss tangent and excellent in removal of the gum residue; a resin sheet having a resin composition layer containing the aforementioned resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device comprising a cured product of the resin composition. The solution of the present invention is a resin composition comprising: (A) An aromatic hydrocarbon resin which contains aromatic rings as single rings or condensed rings and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings; and (B) an active ester-based solidifying agent.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. The present invention further relates to a resin sheet, a printed wiring board, and a semiconductor device each using the resin composition.

Background

In recent years, miniaturization and higher performance of electronic devices have been advanced, and in multilayer printed wiring boards, build-up layers are being multilayered, and miniaturization and higher density of wiring have been demanded, and further, in order to reduce transmission loss, an insulating material having a low dielectric loss tangent has been demanded.

For example, patent document 1 describes a resin composition containing (a) an epoxy resin, (B) an active ester compound, and (C) a residue-inhibiting component, wherein the nonvolatile component of the resin composition is 100 mass%, and the residue-inhibiting component (C) is 0.001 to 10 mass%.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2014-5464.

Disclosure of Invention

Problems to be solved by the invention

When the insulating layer of the multilayer printed wiring board is perforated, a resin residue is generated in the through hole, and it is required to remove the resin residue in the roughening treatment step. However, according to the findings of the present inventors, when a multilayer printed wiring board is produced using a resin composition having a low dielectric loss tangent containing an active ester compound, even if roughening treatment is performed in the through-hole after the opening process of the insulating layer, removal of the residue (resin residue) in the through-hole is sometimes insufficient, and as the through-hole becomes a small diameter, the residue removal becomes more difficult.

Accordingly, an object of the present invention is to provide: a resin composition which can give a cured product having a low dielectric loss tangent and excellent in removal of the gum residue; a resin sheet having a resin composition layer containing the aforementioned resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device comprising a cured product of the resin composition.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by combining a resin composition comprising (a) an aromatic hydrocarbon resin (the aromatic hydrocarbon resin contains an aromatic ring as a single ring or a condensed ring and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings) and (B) an active ester-based curing agent, and have completed the present invention.

Namely, the present invention includes the following,

[1] a resin composition comprising:

(A) An aromatic hydrocarbon resin which contains aromatic rings as single rings or condensed rings and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings; and

(B) An active ester-based solidifying agent;

[2] the resin composition according to the above [1], wherein the component (A) has a structure represented by the following formula (1),

[ chemical formula 1]

(in the formula (1), R ¹¹ Each independently represents a 1-valent group. )

[3] The resin composition according to [1] or [2], wherein the component (A) has a structure represented by the following formula (2),

[ chemical formula 2]

(in the formula (2), R ²¹ Each independently represents a 1-valent group. )

[4] The resin composition according to [1] or [2], wherein the component (A) is represented by the following formula (3),

[ chemical formula 3]

(in the formula (3), R ³¹ Each independently represents a 1-valent group, R ³² Each independently represents a 2-valent hydrocarbon group. n3 represents an integer of 0 to 10. )

[5] The resin composition according to any one of [1] to [4], wherein the component (A) is represented by the following formula (6),

[ chemical formula 4]

(in the formula (6), R ⁶¹ Each independently represents a 1-valent group. n6 represents an integer of 0 to 10. )

[6] The resin composition according to any one of [1] to [5], wherein the group containing an oxygen atom bonded to an aromatic ring is an alkylene oxide group, an alkoxy group or a hydroxyl group;

[7] the resin composition according to any one of [1] to [6], further comprising (C) an epoxy resin;

[8] the resin composition according to [7], wherein the content of the component (A) is 5 to 50 mass% based on 100 mass% of the total content of the component (A) and the component (C);

[9] the resin composition according to any one of [1] to [8], wherein the content of the component (B) is 1% by mass or more and 30% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition;

[10] the resin composition according to any one of [1] to [9], further comprising (D) an inorganic filler;

[11] the resin composition according to [10], wherein the content of the component (D) is 50% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition;

[12] The resin composition according to any one of [1] to [11], which is a resin composition for forming an insulating layer of a multilayer printed wiring board;

[13] the resin composition according to any one of [1] to [12], which is a resin composition for forming an insulating layer having a through hole with a top diameter of 35 μm or less;

[14] the resin composition according to any one of [1] to [13], which is a resin composition for forming an insulating layer having a through hole with a thickness-to-diameter ratio (thickness of insulating layer/top diameter) of 0.5 or more, the through hole having a thickness (μm) of the insulating layer to a top diameter (μm);

[15] a resin sheet, comprising: a support, and a resin composition layer comprising the resin composition according to any one of [1] to [14] provided on the support;

[16] the resin sheet according to [15], wherein the thickness of the resin composition layer is 20 μm or less;

[17] a printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14 ];

[18] a semiconductor device comprising the printed wiring board of [17 ].

ADVANTAGEOUS EFFECTS OF INVENTION

By the present invention, it is possible to provide: a resin composition which can give a cured product having a low dielectric loss tangent and excellent in removal of the gum residue; a resin sheet having a resin composition layer containing the aforementioned resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device comprising a cured product of the resin composition.

Detailed Description

The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented within the scope of the claims and the equivalents thereof.

[ resin composition ]

The resin composition of the present invention contains: (A) An aromatic hydrocarbon resin which contains aromatic rings as single rings or condensed rings and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings; and (B) an active ester-based curing agent. By using such a resin composition layer, the following desired effects of the present invention can be obtained, and a cured product having a low dielectric loss tangent and excellent removal of the gum residue can be obtained. Therefore, the cured product of the resin composition can be used preferably as an insulating layer of a multilayer printed wiring board by utilizing its excellent properties.

The resin composition may contain any component in addition to the components (a) to (B). Examples of the optional components include (C) an epoxy resin, (D) an inorganic filler, (E) a curing agent, (F) a thermoplastic resin, (G) a curing accelerator, and (H) other additives. The components contained in the resin composition of the present invention are described in detail below.

An aromatic hydrocarbon resin comprising an aromatic ring as a single ring or a condensed ring, and having 2 or more groups containing an oxygen atom bonded to the aromatic ring relative to one of the aromatic rings

The resin composition contains (A) an aromatic hydrocarbon resin which contains aromatic rings as single rings or condensed rings and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings. The aromatic ring is easily oxidized by electron donating of an oxygen atom in a group containing an oxygen atom bonded to the aromatic ring. In addition, since 2 or more of the groups are contained with respect to one aromatic ring, the aromatic ring is more easily oxidized. Therefore, the component (a) is easily oxidized, and therefore the removal of the mar from the cured product of the resin composition can be improved.

Herein, the term "aromatic ring" includes: any of aromatic rings as a single ring such as a benzene ring and aromatic rings as condensed rings such as a naphthalene ring. From the viewpoint of remarkably obtaining the desired effect of the present invention, the number of carbon atoms of the aromatic ring contained in each component (a) is preferably 6 or more, more preferably 10 or more, preferably 20 or less, more preferably 14 or less.

Examples of the aromatic ring include monocyclic rings such as benzene rings and biphenyl rings; condensed rings such as naphthalene ring and anthracene ring; for example, condensed rings are preferable from the viewpoint of further improving the removal property of the gum residue. The aromatic ring contained in one molecule of aromatic hydrocarbon resin may be 1 kind or 2 kinds or more.

At least one aromatic ring among the aromatic rings contained in the aromatic hydrocarbon resin as the component (A) has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings. From the viewpoint of significantly obtaining the desired effect of the present invention, the number of groups containing an oxygen atom bonded to an aromatic ring relative to one aromatic ring is preferably 4 or less, more preferably 3 or less, and particularly preferably 2.

The number of aromatic rings having 2 or more "groups containing oxygen atoms bonded to the aromatic rings" per molecule of component (a) is usually 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of significantly obtaining the desired effect of the present invention. The upper limit is not particularly limited, but is preferably 6 or less, more preferably 5 or less, from the viewpoint of suppressing steric hindrance and improving reactivity with the epoxy resin.

Examples of the group containing an oxygen atom bonded to an aromatic ring include an alkylene oxide group, an alkoxy group, a hydroxyl group, and the like. From the viewpoint of significantly obtaining the desired effect of the present invention, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, still more preferably an alkoxy group having 1 to 3 carbon atoms, and particularly preferably an alkoxy group (methoxy group) having 1 carbon atom. From the viewpoint of remarkably obtaining the desired effect of the present invention, the alkylene group in the alkylene oxide group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom (glycidyl ether group).

As the component (a), for example, an aromatic hydrocarbon resin having a structure represented by the following formula (1) is preferable;

[ chemical formula 5]

(in the formula (1), R ¹¹ Each independently represents a 1-valent group).

In the formula (1), R ¹¹ Each independently represents a 1-valent group. The group containing an oxygen atom bonded to the aromatic ring is "-OR in formula (1) ¹¹ ". Examples of the 1-valent group include: a hydrogen atom; an epoxyalkyl group, an optionally substituted alkyl group, and the like. The number of carbon atoms of the alkyl group and the alkyl group in the epoxyalkyl group is the same as that of the aforementioned alkoxy group. Examples of the substituent for the alkyl group include a halogen atom, a hydroxyl group, and an epoxy group. In addition, 2 or more substituents may be bonded to form a ring. Wherein R is from the viewpoint of improving the removal property of the gumming residue ¹¹ The epoxy alkyl group and the hydrogen atom are preferable, the epoxy alkyl group is more preferable, and the glycidyl group is further preferable.

The structure represented by formula (1) is preferably represented by the following formula (2);

[ chemical formula 6]

(in the formula (2), R ²¹ Each independently represents a 1-valent group).

In the formula (2), R ²¹ Represents a 1-valent group, R ²¹ And R in formula (1) ¹¹ The meaning is the same. As in the formula (2), the residue removing property can be further improved by bonding groups containing oxygen atoms bonded to the aromatic ring at the 1-and 6-positions of the naphthalene ring.

The component (a) is preferably, for example, an aromatic hydrocarbon resin represented by the following formula (3);

[ chemical formula 7]

(in the formula (3), R ³¹ Each independently represents a 1-valent group, R ³² Each independently represents a 2-valent hydrocarbon group. n3 represents an integer of 0 to 10).

In the formula (3), R ³¹ Represents a 1-valent group, R ³¹ And R in formula (1) ¹¹ The meaning is the same.

In the formula (3), R ³² Represents a 2-valent hydrocarbon group. The 2-valent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the 2-valent hydrocarbon group is usually 1 or more, and from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more. The upper limit of the number of carbon atoms is preferably 20 or less, 15 or less, or 10 or less from the viewpoint of significantly obtaining the desired effect of the present invention.

As R ³² Specific examples of (a) include the following 2-valent hydrocarbon groups.

[ chemical formula 8]

。

In the formula (3), n3 represents an integer of 0 to 10. From the viewpoint of significantly obtaining the desired effect of the present invention, n3 is preferably 0 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less.

The aromatic hydrocarbon resin represented by the formula (3) is preferably an aromatic hydrocarbon resin represented by the following formula (4);

[ chemical formula 9]

(in the formula (4), R ⁴¹ Each independently represents a 1-valent group, R ⁴² Each independently represents an alkylene group. n4 represents an integer of 0 to 10).

In the formula (4), R ⁴¹ Represents a 1-valent group, R ⁴¹ And R in formula (1) ¹¹ The meaning is the same.

In the formula (4), R ⁴² Represents an alkylene group. The number of carbon atoms of the alkylene group is preferably 10 or less, more preferably 6 or less, further preferably 3 or less, and may be 1 or more for the lower limit. Among them, methylene and dimethylethylene are preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.

In the formula (4), n4 represents an integer of 0 to 10, and n4 has the same meaning as n3 in the formula (3).

The phenylene group in the formula (4) is preferably in the 1-position and 4-position and 2 groups represented by R ⁴² An alkylene linkage is represented.

The aromatic hydrocarbon resin represented by the formula (4) is preferably an aromatic hydrocarbon resin represented by the following formula (5);

[ chemical formula 10]

(in the formula (5), R ⁵¹ Each independently represents a 1-valent group, R ⁵² Each independently represents an alkylene group. n5 represents an integer of 0 to 10).

In the formula (5), R ⁵¹ Represents a 1-valent group, R ⁵¹ And R in formula (1) ¹¹ The meaning is the same.

In the formula (5), R ⁵² Represents an alkylene group. R is R ⁵² R in the formula (4) ⁴² The meaning is the same.

In the formula (5), n5 represents an integer of 0 to 10, and n5 has the same meaning as n3 in the formula (3).

Among them, the component (a) is preferably an aromatic hydrocarbon resin represented by the following formula (6);

[ chemical formula 11]

(in the formula (6), R ⁶¹ Each independently represents a 1-valent group. n6 represents an integer of 0 to 10).

In the formula (6), R ⁶¹ Represents a 1-valent group, R ⁶¹ And R in formula (1) ¹¹ The meaning is the same.

In the formula (6), n6 represents an integer of 0 to 10, and n6 has the same meaning as n3 in the formula (3).

Examples of the commercial product of the component (a) include: "ESN375", "SN395" manufactured by Nippon Kagaku Co., ltd., and "HP4032", "HP4032D", "HP4032SS", "HP4032H", "HP4700", "HP4710" manufactured by DIC Co., ltd., NC3500 "manufactured by Nippon chemical Co., ltd.

The aromatic hydrocarbon resin as the component (A) may be used singly or in combination of two or more.

(A) When the group containing an oxygen atom bonded to an aromatic ring of the component (a) includes an epoxy group, the epoxy equivalent of the component (a) is preferably 50 to 5000g/eq, more preferably 50 to 3000g/eq, still more preferably 80 to 2000g/eq, still more preferably 90 to 1000g/eq, from the viewpoint of remarkably obtaining the desired effect of the present invention. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

(A) When the group containing an oxygen atom bonded to an aromatic ring of the component (a) includes a hydroxyl group, the hydroxyl equivalent of the component (a) is preferably 50g/eq. Or more, more preferably 60g/eq. Or more, still more preferably 70g/eq. Or more, and preferably 250g/eq. Or less, more preferably 150g/eq. Or less, particularly preferably 120g/eq. Or less, from the viewpoint of improving the crosslinking density of the insulating layer which is a cured product of the resin composition layer and remarkably obtaining the desired effect of the present invention. The hydroxyl equivalent is the mass of the resin containing 1 equivalent of hydroxyl groups.

When the number of the oxygen atom-containing groups bonded to the aromatic ring of the component (a) includes a hydroxyl group, the number of the oxygen atom-containing groups bonded to the aromatic ring of the component (a) is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less, from the viewpoint of obtaining a cured product having more excellent scum removability, when the number of the epoxy groups of the epoxy resin (C) is 1. The term "(C) epoxy resin epoxy number" as used herein means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the component (C) in the resin composition by the epoxy equivalent weight. The term "number of groups containing an oxygen atom bonded to an aromatic ring" in the component (a) means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the component (a) existing in the resin composition by the equivalent weight of the groups containing an oxygen atom bonded to an aromatic ring.

From the viewpoint of obtaining a cured product excellent in the removal of the offset residue, the content of the component (a) is preferably 0.5 mass% or more, more preferably 0.8 mass% or more, still more preferably 1 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass% or 5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition;

in the present invention, unless otherwise specifically indicated, the content of each component in the resin composition refers to a value obtained by setting the nonvolatile content in the resin composition to 100 mass%.

In addition, from the viewpoint of obtaining a cured product having more excellent removal of the gum residue, the content of the component (a) is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less, based on 100% by mass of the total content of the component (a) and the epoxy resin (C) described later.

Active ester curing agent

The resin composition contains (B) an active ester curing agent. When an active ester-based curing agent is used, the dielectric loss tangent can be generally reduced, but on the other hand, the removal of the cement residue is poor. However, since the resin composition of the present invention contains the component (a), the following resin composition can be obtained: a cured product having excellent removal of the cement residue while reducing the dielectric loss tangent can be obtained.

As the active ester-based curing agent (B), compounds having 2 or more ester groups having high reactivity in one molecule, such as phenol esters (phenol esters), thiophenol esters (thiophenol esters), N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, are generally preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or the naphthol compound include: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol compounds, phenol novolac (phenol novolac), and the like. The "dicyclopentadiene type phenol compound" herein means a phenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, dicyclopentadiene-type active ester-based curing agents, active ester-based curing agents containing naphthalene structures, active ester-based curing agents containing an acetylated product of a phenol-formaldehyde resin, and active ester-based curing agents containing a benzoylate of a phenol-formaldehyde resin are preferable, and among these, active ester-based curing agents containing naphthalene structures and dicyclopentadiene-type active ester-based curing agents are more preferable, and dicyclopentadiene-type active ester-based curing agents are still more preferable. The dicyclopentadiene type active ester-based curing agent preferably contains an active ester-based curing agent having a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" means a 2-valent structural unit formed from phenylene-dicyclopentylene-phenylene.

As the commercial product of the active ester curing agent (B), examples of the active ester curing agent containing dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB8000L-65TM" (manufactured by DIC Co.); examples of the active ester-based curing agent containing a naphthalene structure include "EXB8150-60T" and "EXB9416-70BK" (manufactured by DIC Co., ltd.); examples of the active ester-based curing agent containing an acetylation compound of a phenol novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester-based curing agent containing a benzoyl compound of a phenol novolac resin include "YLH1026" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent which is an acetylation product of a phenol novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester-based curing agent which is a benzoyl compound of the phenol-formaldehyde resin include "YLH1026" (manufactured by Mitsubishi chemical corporation), "YLH1030" (manufactured by Mitsubishi chemical corporation), "YLH1048" (manufactured by Mitsubishi chemical corporation); etc.

(B) The ratio of the amount of the active ester curing agent to the amount of the components (A) and (C) is defined as [ (total of the epoxy groups of the components (A) and (C)) ]: the ratio of [ total number of reactive groups of the active ester-based curing agent ] is preferably 1:0.01 to 1:5, more preferably 1:0.05 to 1:2, further preferably 1:0.1 to 1:1.8. the reactive group of the active ester-based curing agent means an active ester group. The total number of epoxy groups in the components (a) and (C) is a value obtained by adding all the values obtained by dividing the mass of the solid components of each component by the epoxy equivalent; the total number of reactive groups of the active ester-based curing agent is a value obtained by adding up the values obtained by dividing the solid content mass of each active ester-based curing agent by the equivalent of the reactive groups, to all the active ester-based curing agents. When the amount ratio of the epoxy resin to the active ester-based curing agent is in the above range, the heat resistance of the cured product of the resin composition is further improved.

The content of the active ester-based curing agent (B) is preferably 1 mass% or more, more preferably 3 mass% or more, and still more preferably 5 mass% or more, based on 100 mass% of the nonvolatile components in the resin composition. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. When the content of the component (B) is within the above range, a cured product excellent in the removal of the gum residue can be obtained.

Epoxy resin (C)

The resin composition may contain (C) an epoxy resin. However, the component (C) does not include a substance belonging to the component (A).

Examples of the epoxy resin (C) include: a bisxylenol (bispyrinol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac (phenolic novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidol amine type epoxy resin, a glycidol ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a cycloaliphatic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, and the like. The epoxy resin may be used alone or in combination of two or more.

The resin composition preferably contains, as the (C) epoxy resin, an epoxy resin having 2 or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the (C) epoxy resin.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). As the (C) epoxy resin, the resin composition may contain only a liquid epoxy resin or only a solid epoxy resin, but preferably contains a liquid epoxy resin and a solid epoxy resin in combination. By using a liquid epoxy resin and a solid epoxy resin in combination as the (C) epoxy resin, the flexibility of the resin composition layer can be improved, or the breaking strength of a cured product of the resin composition layer can be improved.

As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having 2 or more epoxy groups in one molecule is more preferable. The term "aromatic-based" epoxy resin as used herein means an epoxy resin having an aromatic ring in its molecule.

As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferable; more preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy resin.

Specific examples of the liquid epoxy resin include: "828US", "jER828EL", "825", "Epikote 828EL" by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ZX1059" manufactured by Nippon iron gold chemical Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Kagaku Kogyo Co., ltd; "PB-3600" manufactured by Kagaku Kogyo Co., ltd. (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Ten Kagaku Kogyo Co., ltd. One kind of them may be used alone, or two or more kinds may be used in combination.

As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferable.

The solid epoxy resin is preferably a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, or a tetraphenylethane-type epoxy resin, and more preferably a binaphthol-type epoxy resin, a naphthalene-type epoxy resin, a bisphenol AF-type epoxy resin, or a naphthylene ether-type epoxy resin.

Specific examples of the solid epoxy resin include: "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Co., ltd; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical medicine corporation; "ESN475V" manufactured by Nippon iron gold chemical Co., ltd. (naphthol type epoxy resin); "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon iron gold chemical Co., ltd; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX4000HK" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company, and the like. One kind of them may be used alone, or two or more kinds may be used in combination.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the (C) epoxy resin, the ratio of their amounts (liquid epoxy resin: solid epoxy resin) is preferably 1 in terms of mass ratio: 1 to 1:20, more preferably 1:1 to 1:15, particularly preferably 1:1 to 1:10. the desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range. In addition, in general, when used in the form of a resin sheet, moderate adhesion can be imparted. In addition, in general, when used in the form of a resin sheet, sufficient flexibility can be obtained, and the handleability is improved. In addition, generally, a cured product having sufficient breaking strength can be obtained.

(C) The epoxy equivalent of the epoxy resin is preferably 50 to 5000g/eq, more preferably 50 to 3000g/eq, still more preferably 80 to 2000g/eq, still more preferably 110 to 1000g/eq. When the amount is within the above range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (C) epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500.

The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).

When the resin composition contains (C) an epoxy resin, the content of (C) is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is preferably 30 mass% or less, more preferably 25 mass% or less, and particularly preferably 20 mass% or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

Inorganic filler (D)

The resin composition may contain (D) an inorganic filler. As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include: silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, etc. Among these, silica is particularly preferable. Examples of the silica include: amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferable as silica. (D) The inorganic filler may be used alone or in combination of two or more.

Examples of the commercial product of the inorganic filler (D) include: "SP60-05", "SP507-05" manufactured by Nippon iron gold Material Co., ltd; "YC100C", "YA050C-MJE", "YA010C" manufactured by Admatechs company; "UFP-30" manufactured by Denka Co., ltd; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co., ltd; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; etc.

From the viewpoint of significantly obtaining the desired effect of the present invention, the average particle diameter of the (D) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less.

(D) The average particle size of the inorganic filler material can be determined using a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be measured by the following means: the particle size distribution of the inorganic filler was prepared based on volume by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was used as the average particle size. As the measurement sample, a sample obtained by weighing 100mg of an inorganic filler, 0.1g of a dispersant (SN 9228 made by Sannopco Co., ltd.) and 10g of methyl ethyl ketone into a vial (visual container) and dispersing the mixture for 20 minutes by ultrasonic waves was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus (SALD-2200 made by Shimadzu corporation) was used to measure the particle size distribution in a batch cell (batch cell) and calculate the average particle size as the median particle size.

The specific surface area of the (D) inorganic filler is preferably 1m from the viewpoint of easy control of the shape of the through hole and realization of a good shape ² Preferably at least/g, more preferably at least 2m ² Preferably at least 5m ² And/g. The upper limit is not particularly limited, but is preferably 60m ² Per gram of less than 50m ² /g or less than 40m ² And/g or less. The specific surface area of the inorganic filler can be measured by the BET method.

The inorganic filler (D) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include: fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of two or more kinds.

Examples of the commercial product of the surface treatment agent include: "KBM403" from Xinyue chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" from Xinyue chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" from Xinyue chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" from Xinyue chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" from Xinyue chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" from Xinyue chemical industry Co., ltd. (long chain epoxy type silane coupling agent), and "KBM-7103" from Xinyue chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane) and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably limited to a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of a surface-treating agent, preferably 0.2 to 3 parts by mass, and preferably 0.3 to 2 parts by mass, based on 100 parts by mass of the inorganic filler.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m ² The above is more preferably 0.1mg/m ² The above is more preferably 0.2mg/m ² The above. On the other hand, from the viewpoint of suppressing the rise in melt viscosity of the resin varnish and in melt viscosity in sheet form, it is preferably 1mg/m ² Hereinafter, more preferably 0.8mg/m ² Hereinafter, it is more preferably 0.5mg/m ² The following is given.

The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing was performed at 25 ℃ for 5 minutes. The supernatant is removed, the solid component is dried, and then the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.

When the resin composition contains (D) the inorganic filler, the content of (D) the inorganic filler is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 65 mass% or more, preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 80 mass% or less, relative to 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of reducing the dielectric loss tangent of the insulating layer.

Curing agent (E)

The resin composition may contain (E) a curing agent. However, the (E) curing agent does not include the (B) active ester curing agent. Examples of the curing agent (E) include: phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate-based curing agents, carbodiimide-based curing agents, and the like. Among them, from the viewpoint of improving insulation reliability, the (E) curing agent is preferably any one or more of a phenol curing agent, a naphthol curing agent, a cyanate curing agent, and a carbodiimide curing agent, and more preferably contains a phenol curing agent. The curing agent may be used singly or in combination of two or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenol structure or a naphthol-based curing agent having a phenol structure is preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent containing a triazine skeleton is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example: "MEH-7700", "MEH-7810", "MEH-7851" made by Ming He Chemicals, japan chemical company, "NHN", "CBN", "GPH", and "SN170", "SN180", "SN190", "SN475", "SN485", "SN 495V", "SN375", "SN395" made by Nissan Chemie, DIC "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" made by Nissan chemical company.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer, and "P-d" and "F-a" manufactured by four chemical industries, inc.

Examples of the cyanate-based curing agent include: bisphenol A dicyanate, polyphenol cyanate (polyphenol cyanate), oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate phenyl-1- (methylethylene)) benzene, bis (4-cyanate phenyl) sulfide, bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins, prepolymers obtained by partially triazinizing these cyanate resins, and the like. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" manufactured by Lonza Japan (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230" and "BA230S75" (prepolymer in which part or all of bisphenol a dicyanate is triazinized to form a trimer).

Specific examples of the carbodiimide-based curing agent include "V-03", "V-07", which are manufactured by Nisshink chemical (Nisshinbo Chemical).

When the resin composition contains the curing agent (E), the ratio of the amounts of the components (A) and (C) to the curing agent (E) is defined as the total number of epoxy groups of the components (A) and (C): the ratio of [ total number of reactive groups of curing agent ] is preferably 1:0.01 to 1:2, more preferably 1:0.01 to 1:1, further preferably 1:0.03 to 1:0.5. the reactive group of the curing agent herein means an active hydroxyl group or the like, and is different depending on the type of the curing agent. The total number of reactive groups of the curing agent is a sum of the solid content mass of each curing agent divided by the equivalent amount of reactive groups for all the curing agent. By setting the amount ratio of the components (a) and (C) to the curing agent to the above range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains the (B) active ester curing agent and the (E) curing agent, the ratio of the amounts of the (A) and (C) components to the (B) active ester curing agent and the (E) curing agent is [ (the total of the epoxy groups of the (A) and (C) components ]: the ratio of [ (total number of reactive groups of the (B) and (E) components ] is preferably 1:0.01 to 1:5, more preferably 1:0.05 to 1:2, further preferably 1:0.1 to 1:1. when the amount ratio is in the above range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (E) a curing agent, the content of (E) the curing agent is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and still more preferably 0.5 mass% or more, based on 100 mass% of the nonvolatile components in the resin composition. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and still more preferably 1 mass% or less. When the content of the curing agent (E) is within the above range, the heat resistance of the cured product of the resin composition is further improved.

Thermoplastic resin (F)

The resin composition may contain (F) a thermoplastic resin. Examples of the thermoplastic resin as the component (F) include: phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. Among them, the phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and the viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to a conductor layer. In addition, the thermoplastic resin may be used singly or two or more kinds may be used in combination.

Examples of the phenoxy resin include: a phenoxy resin having 1 or more kinds of skeletons selected from the group consisting of bisphenol a skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenol skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.

Specific examples of the phenoxy resin include: "1256" and "4250" both made by Mitsubishi chemical corporation (phenoxy resins each having a bisphenol A skeleton); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Kagaku Kogyo Co., ltd; "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi chemical corporation; etc.

Examples of the polyvinyl acetal resin include: the polyvinyl formal resin and the polyvinyl butyral resin are preferably polyvinyl butyral resins. Specific examples of the polyvinyl acetal resin include: "Denka butyl 4000-2", "Denka butyl 5000-A", "Denka butyl 6000-C", "Denka butyl 6000-EP" manufactured by electric chemical industries, inc.; S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, manufactured by the water chemical industry Co., ltd; etc.

Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by new japan physicochemical company. Specific examples of the polyimide resin include linear polyimides (polyimides described in JP 2006-37083A) obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and modified polyimides such as polyimides containing a polysiloxane skeleton (polyimides described in JP 2002-12667A, JP 2000-319386A and the like).

Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical company.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.

Specific examples of the polyphenylene ether resin include a low polyphenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi gas chemical corporation.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (F) thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

When the resin composition contains (F) a thermoplastic resin, the content of (F) the thermoplastic resin is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, still more preferably 0.3 mass% or more, preferably 1.5 mass% or less, still more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.

(G) curing accelerator

The resin composition may contain (G) a curing accelerator. Examples of the curing accelerator (G) include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include: triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphine thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include: trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene and the like, preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5, 4, 0) -undecene.

Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylguanidine, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, preferably dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.

Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include: cobalt (II) acetylacetonate, cobalt (III) acetylacetonate and other organic cobalt complexes, copper (II) acetylacetonate and other organic copper complexes, zinc (II) acetylacetonate and other organic zinc complexes, iron (III) acetylacetonate and other organic iron complexes, nickel (II) acetylacetonate and other organic nickel complexes, manganese (II) acetylacetonate and other organic manganese complexes, and the like. Examples of the organic metal salt include: zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains (G) a curing accelerator, the content of the (G) curing accelerator is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, preferably 3 mass% or less, still more preferably 2 mass% or less, and still more preferably 1.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.

Additive (H) optionally

The resin composition may contain, in addition to the above-described components, any additives as optional components. Examples of such additives include: an organic filler material; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; resin additives such as flame retardants, thickeners, defoamers, leveling agents, adhesion imparting agents, and colorants; etc. These additives may be used singly or in combination of two or more.

Physical Properties and use of resin composition

The cured product obtained by heat-curing the resin composition at 100℃for 30 minutes and then at 170℃for 30 minutes generally exhibits excellent removal of the gum residue. Therefore, even if a through hole is formed in the cured product, an insulating layer having a maximum grain length of less than 5 μm at the bottom of the through hole is obtained. The removal of the gum residue can be measured by the method described in examples described below.

The cured product obtained by heat curing the resin composition at 200℃for 90 minutes exhibits such a characteristic that the dielectric loss tangent is low. Thus, an insulating layer having a low dielectric loss tangent was obtained. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.008 or less, and still more preferably 0.005 or less. The lower limit is not particularly limited, and may be 0.0001 or more. The dielectric loss tangent can be measured by the method described in examples described below.

The resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and excellent in removal of the gum residue. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for an insulating layer of a multilayer printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer having excellent component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

In particular, the resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and excellent in removal of the offset, and thus can form an insulating layer having a small diameter of the through hole. Therefore, the resin composition is suitable as a resin composition for forming an insulating layer having a through hole (a resin composition for forming an insulating layer having a through hole), particularly suitable as a resin composition for forming an insulating layer having a through hole with a top diameter of 35 μm or less; the resin composition is particularly suitable for forming an insulating layer having a through-hole having a thickness-to-diameter ratio (thickness/top diameter of the insulating layer) of 0.5 or more. Here, the term "top diameter" means the maximum diameter of an opening formed on the opposite side of the through-hole from the substrate when the through-hole is formed on the insulating layer on the substrate; the "thickness of the insulating layer" means the thickness of the entire insulating layer, that is, the depth of the through hole.

The thickness-to-diameter ratio (thickness/top diameter) of the insulating layer (μm) to the top diameter (μm) is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, preferably 3 or less, still more preferably 2 or less, and still more preferably 1 or less from the viewpoint of downsizing and higher performance of the electronic device.

[ resin sheet ]

The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 40 μm or less, more preferably 35 μm or less, and even more preferably 25 μm or less and 20 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product excellent in insulation even if it is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be generally 3 μm or more, 5 μm or more, 7 μm or more, or the like.

Examples of the support include: the film, metal foil, and release paper formed of a plastic material are preferably a film or a metal foil formed of a plastic material.

When a film made of a plastic material is used as the support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN") and the like, acrylic plastics such as polycarbonate (hereinafter, abbreviated as "PC"), polymethyl methacrylate (PMMA) and the like, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of copper as a single metal may be used, or a foil formed of an alloy of copper with other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. The release agent used in the release layer of the support having a release layer includes, for example, 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. The support having a release layer may be a commercially available support, and examples thereof include: PET films having a release layer containing an alkyd-based release agent as a main component, namely, "SK-1", "AL-5", "AL-7" by Leideaceae, and "LUMIRROR T60" by Toli, and "Purex" by Di people, and "Unipel" by UNITKA, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further include other layers as needed. Examples of the other layer include: a protective film or the like provided on a surface of the resin composition layer which is not bonded to the support (i.e., a surface on the opposite side of the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer or occurrence of damage on the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by: a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied to a support by using a die coater or the like, and then dried to form a resin composition layer.

Examples of the organic solvent include: ketones such as acetone, methyl Ethyl Ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide and dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying can be performed by a known method such as heating and blowing hot air. The drying conditions are not particularly limited, and the resin composition layer may be dried so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing 30 to 60 mass% of the organic solvent, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

The resin sheet may be wound into a roll for storage. When the resin sheet has a protective film, the protective film can be peeled off for use.

[ printed wiring Board ]

The printed wiring board of the present invention comprises an insulating layer formed of a cured product of the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by using the resin sheet described above and using a method comprising the steps (I) and (II) described below,

(I) A step of laminating the resin composition layer of the resin sheet on the inner substrate so as to bond the resin composition layer to the inner substrate;

(II) a step of thermally curing the resin composition layer to form an insulating layer.

The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include: glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene oxide substrates, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate product to be further formed into an insulating layer and/or a conductor layer at the time of manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.

Lamination of the inner substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet against the inner substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS panel or the like) or a metal roller (SUS roller) or the like is cited. It is preferable that the heat and pressure bonding member is not directly pressed against the resin sheet, but is pressed through an elastic material such as heat-resistant rubber in order to make the resin sheet sufficiently follow the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by vacuum lamination. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include: a vacuum laminator manufactured by the company name machine, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, a batch vacuum laminator, and the like.

After lamination, the laminated resin sheets may be smoothed by pressing the thermocompression bonding member from the support body side at normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing process may be set to the same conditions as the above-described laminated thermocompression bonding conditions. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.

The support may be removed between the step (I) and the step (II), or may be removed after the step (II).

In the step (II), the resin composition layer is thermally cured to form an insulating layer.

The heat curing condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition and the like, and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 200 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 90 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes) at a temperature of 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 115 ℃ or less, more preferably 70 ℃ or more and 110 ℃ or less) before the resin composition layer is thermally cured.

In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. The steps (III) to (V) may be performed according to various methods known to those skilled in the art, which are available in the production of printed wiring boards. In the case where the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). The insulating layer and the conductor layer in the steps (II) to (V) may be repeatedly formed as needed to form a multilayer wiring board.

The step (III) is a step of forming holes such as through holes and through holes in the insulating layer by forming holes in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size or shape of the hole may be appropriately determined according to the design of the printed wiring board.

The top diameter of the through hole is preferably 70 μm or less, more preferably 60 μm or less, even more preferably 55 μm or less, or 35 μm or less, from the viewpoint of downsizing and higher performance of the electronic device. The lower limit is not particularly limited, and may be 10 μm or more. The top diameter of the via may be determined, for example, using SEM.

The step (IV) is a step of roughening the insulating layer. In this step (IV), usually, the removal of the gum residue is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, preferably an alkali solution, and more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN, inc. The swelling treatment with the swelling liquid is not particularly limited, and for example, the insulating layer may be immersed in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by ATOTECH JAPAN corporation. The neutralization solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN corporation. The neutralization solution-based treatment can be performed by immersing the treated surface, on which the roughening treatment by the oxidizing agent is completed, in the neutralization solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object subjected to the roughening treatment by the oxidizing agent in a neutralizing liquid at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400nm or less, more preferably 350nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be preferably 0.5nm or more, more preferably 1nm or more, and the like. The root mean square roughness (Rq) of the roughened insulating layer surface is preferably 400nm or less, more preferably 350nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be preferably 0.5nm or more, more preferably 1nm or more, and the like. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises 1 or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of 2 or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, and still more preferably a single metal layer of copper is preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more single metal layers or alloy layers each made of a different metal or alloy are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a half-addition method or a full-addition method, and it is preferable to form the conductor layer by a half-addition method from the viewpoint of ease of manufacturing. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.

First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

Since the resin sheet of the present invention provides an insulating layer having excellent embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be provided with: an insulating layer which is a cured product of a resin composition layer of a resin sheet, and a buried wiring layer buried in the insulating layer.

[ semiconductor device ]

The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

The semiconductor device may be: various semiconductor devices are available for use in electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, electric trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive position of a printed wiring board. The "on position" refers to a "position in the printed wiring board where an electrical signal is transmitted", and the position may be a surface or a buried position. The semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

The mounting method of the semiconductor chip in manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip is effectively functioning, and specifically, there is given: a wire bonding mounting method, a flip chip mounting method, a mounting method using a solderless build-up layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using a solderless build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board, and the semiconductor chip is connected to wiring on the printed wiring board".

Examples (example)

The present invention will be specifically described below with reference to examples. The present invention is not limited to the following examples. In the following description, unless otherwise explicitly indicated, "part" and "%" indicating amounts refer to "part by mass" and "% by mass", respectively. Unless otherwise specifically indicated, the operations described below are performed under normal temperature and normal pressure conditions.

Example 1

10 parts of bisphenol type epoxy resin (1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) and 30 parts of naphthol type epoxy resin (ESN 475V, manufactured by Nippon iron and gold chemical Co., ltd., epoxy equivalent 330) were dissolved in 40 parts of solvent naphtha by heating while stirring. It was cooled to room temperature to prepare a dissolved composition of the epoxy resin (X).

In addition, 10 parts of an aromatic hydrocarbon resin (ESN 375, manufactured by new japanese gold chemical company, having an epoxy equivalent of about 171) having a structure shown below was dissolved in 10 parts of MEK under heating while stirring, and then cooled to room temperature to prepare a solution of an aromatic hydrocarbon resin (Y).

[ chemical formula 12]

(n represents an integer of 1 to 10).

In the epoxy resin (X) dissolved composition, 5 parts of phenoxy resin (YX 7553BH30, 1:1 solution of 30% by mass of solid component MEK and cyclohexanone, 5 parts of phenol curing agent (LA-3018-50P, about 151 active group equivalent, 50% by mass of 2-methoxypropanol solution, DIC Co., ltd.), 50 parts of active ester curing agent (HPC-8000-65T, about 223 active group equivalent, 65% by mass of solid component toluene solution), 5 parts of curing accelerator (1-benzyl-2-phenylimidazole (1B 2PZ, 1% by mass of MEK solution), 5 parts of spherical silica surface-treated with amine alkoxysilane compound (KBM 573, about 0.77 μm average particle diameter, about SO-C2, manufactured by Admatechs Co., ltd.), and 20 parts of aromatic resin (Y) were mixed, and a varnish was prepared by a high-speed spin mixer.

As a support, a polyethylene terephthalate film (AL 5, manufactured by linde co., thickness 38 μm, PET film) having a release layer was prepared. The resin varnish was uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 15. Mu.m. Then, the resin varnish was dried at 80 to 100 ℃ (average 90 ℃) for 3 minutes to prepare a resin sheet comprising a support and a resin composition layer.

Example 2

In example 1, 50 parts of an active ester-based curing agent (toluene solution having an active group equivalent of about 223 and 65% by mass of solid content, manufactured by DIC corporation, "HPC-8000L-65T"), was changed to 50 parts of an active ester-based curing agent (toluene-MEK mixed solution having an active group equivalent of 220 and 65% by mass of solid content, manufactured by DIC corporation). Except for the above, a resin varnish and a resin sheet were produced in the same manner as in example 1.

Example 3

In example 1, 50 parts of an active ester-based curing agent (DIC "HPC-8000-65T", active group equivalent weight of about 223, toluene solution with 65% solid content by mass) was changed to 55 parts of an active ester-based curing agent (DIC "EXB8150-60T", active group equivalent weight of 230, toluene solution with 60% solid content). Except for the above, a resin varnish and a resin sheet were produced in the same manner as in example 1.

Example 4

While stirring, 10 parts of bisphenol type epoxy resin (1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) ("ZX 1059" manufactured by Nippon Kagaku Co., ltd.) and 20 parts of naphthol type epoxy resin (ESN 475V manufactured by Nippon Kagaku Co., ltd., epoxy equivalent 330) were dissolved in 40 parts of solvent naphtha by heating. Cooling to room temperature to prepare a dissolved composition of epoxy resin (X2);

while stirring, 20 parts of an aromatic hydrocarbon resin (ESN 375, manufactured by Nippon Kagaku Co., ltd., epoxy equivalent of about 171) was dissolved in 20 parts of MEK by heating, and the solution was cooled to room temperature to prepare a solution of an aromatic hydrocarbon resin (Y2).

In this epoxy resin (X2) dissolved composition, 5 parts of a phenoxy resin (YX 7553BH30, mitsubishi chemical corporation, 1:1 solution of 30% by mass of MEK and cyclohexanone), 80 parts of an active ester-based curing agent (EXB 8150-60T, 230 active group equivalents, 60% by mass of toluene solution, and 1-benzyl-2-phenylimidazole (1B 2 PZ), 5 parts of a curing accelerator (10% by mass of MEK solution), 250 parts of spherical silica surface-treated with an amine-based alkoxysilane compound (KBM 573, manufactured by Xinyue chemical industries, inc.), and 40 parts of an aromatic hydrocarbon resin (Y2) solution were mixed, and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Further, a resin sheet was produced in the same manner as in example 1.

Example 5

In the case of the embodiment of the present invention in which the sample is a solid,

1) The amount of 20 parts of aromatic hydrocarbon resin (ESN 375, manufactured by Nippon iron and gold chemical Co., ltd., epoxy equivalent of about 171) was changed from 20 parts to 5 parts,

2) The amount of naphthol type epoxy resin (ESN 475V, manufactured by Nippon Kagaku Co., ltd., epoxy equivalent weight: about 330) was changed from 30 parts to 40 parts,

3) The amount of spherical silica (average particle diameter: 0.77 μm, manufactured by Admatechs Co., ltd. "SO-C2") surface-treated with an amine-based alkoxysilane compound (manufactured by Xinteichi chemical Co., ltd. "KBM 573") was changed from 220 parts to 230 parts;

except for the above, a resin varnish and a resin sheet were produced in the same manner as in example 1.

Example 6

While stirring, 10 parts of bisphenol type epoxy resin (ZX 1059, a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) and 50 parts of naphthol type epoxy resin (ESN 475V, epoxy equivalent about 330, manufactured by Nippon iron and gold chemical Co., ltd.) were dissolved in 40 parts of solvent naphtha by heating. Cooling to room temperature to prepare a dissolved composition of epoxy resin (X3);

while stirring, 3 parts of an aromatic hydrocarbon resin (New Zealand gold chemical Co., ltd. "SN395-50M", active group equivalent 107, used as a 50% solid solution in MEK) and 5 parts of an aromatic hydrocarbon resin (New Zealand gold chemical Co., ltd. "ESN375", epoxy equivalent 171) were heated and dissolved in 10 parts of MEK, and then cooled to room temperature to prepare a solution of an aromatic hydrocarbon resin (Y3).

[ chemical formula 13]

(n represents an integer of 1 to 10).

In the epoxy resin (X3) dissolved composition, 5 parts of phenoxy resin (1:1 solution of 30 mass% of MEK and cyclohexanone, manufactured by Mitsubishi chemical corporation), 2 parts of phenol curing agent (LA-3018-50P, manufactured by DIC corporation, active group equivalent of about 151, 50% of 2-methoxypropanol solution, manufactured by solid component 50%), 55 parts of active ester curing agent (EXB 8150-60T, manufactured by DIC corporation, active group equivalent of 230, 60% of toluene solution, and solid component), 5 parts of curing accelerator (1-benzyl-2-phenylimidazole (1B 2 PZ), 10 mass% of MEK solution, manufactured by Santeichum chemical corporation), 240 parts of spherical silica (average particle size of 0.77 μm, manufactured by Admaths corporation, "SO-C2"), and 13 parts of aromatic resin (Y3) were mixed, and the resin was uniformly dispersed by a high-speed spin mixer. Further, a resin sheet was produced in the same manner as in example 1.

Comparative example 1

In the case of the embodiment 1 of the present invention,

1) The amount of spherical silica (average particle diameter: 0.77 μm, manufactured by Admatechs Co., ltd. "SO-C2") surface-treated with an amine-based alkoxysilane compound (manufactured by Xinyue chemical industry Co., ltd. "KBM 573") was changed from 220 parts to 240 parts,

2) The amount of naphthol type epoxy resin (ESN 475V, manufactured by Nippon Kagaku Co., ltd., epoxy equivalent weight: about 330) was changed from 40 parts to 50 parts,

3) 10 parts of an unused aromatic hydrocarbon resin (ESN 375, manufactured by Nippon iron and gold chemical Co., ltd., epoxy equivalent of about 171);

Comparative example 2

except for the above, a resin varnish and a resin sheet were produced in the same manner as in example 2.

Comparative example 3

except for the above, a resin varnish and a resin sheet were produced in the same manner as in example 3.

< evaluation of the removal Property of the gum residue >

(1) Base treatment of inner layer substrates

As the inner layer substrate, a glass cloth base epoxy resin double-sided copper-clad laminate having copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8mm, manufactured by sonchikuwa corporation, "R1515A") was prepared. The copper foil on the surface of the inner layer substrate was etched with a copper etching amount of 1 μm using a microetching agent (CZ 8101 manufactured by MEC corporation), and roughened. Then, drying was performed at 190℃for 30 minutes.

(2) Lamination and curing of resin sheets

The resin sheets obtained in the examples and comparative examples were laminated on both sides of the inner layer substrate using a batch vacuum press laminator (grade 2 stack laminator "CVP700" manufactured by Nikko-Materials Co., ltd.) so that the resin composition layer was bonded to the inner layer substrate. The lamination is carried out by: decompressing for 30 seconds to make the air pressure below 13hPa, and then crimping for 30 seconds under the conditions that the temperature is 100 ℃ and the pressure is 0.74 MPa;

Next, the laminated resin sheet was subjected to hot pressing at 100 ℃ under a pressure of 0.5MPa for 60 seconds under atmospheric pressure to smooth it. Then, the mixture was put into an oven at 100℃for 30 minutes, and then transferred into an oven at 170℃for 30 minutes, thereby forming an insulating layer.

(3) And (3) forming a through hole:

CO manufactured by Via Mechanics Co ₂ A laser processing machine (LK-2K 212/2C) processes the insulating layer at a frequency of 2000Hz with a pulse width of 6 μsec, an output of 0.24mJ, and an irradiation (shot) number of 3, forming a through hole with a top diameter of 25 μm in the surface of the insulating layer and a diameter of 19 μm in the bottom surface of the insulating layer. Further, the PET film of the support is peeled off.

(4) Roughening treatment

The inner substrate was immersed in Swelling Dip Securiganth P of ATOTECH JAPAN Co., ltd. As a swelling liquid at 60℃for 5 minutes. Next, the mixture was subjected to a roughening treatment at 80℃in a roughening treatment liquid (KMnO) of Concentrate Compact P (ATOTECH JAPAN Co., ltd.) ₄ :60g/L, naOH:40g/L aqueous solution) for 20 minutes. Finally, at 40 DEG CThe resultant solution was immersed in Reduction Solution Securiganth P of ATOTECH JAPAN Co., ltd for 5 minutes.

(5) Evaluation of residue at bottom of through hole

Observing the periphery of the bottom of the through hole by using a Scanning Electron Microscope (SEM), measuring the maximum glue residue length from the wall surface of the bottom of the through hole according to the obtained image, and evaluating according to the following standard;

o: the maximum glue residue length is less than 5 mu m

X: the maximum gum residue length is more than 5 mu m.

< determination of dielectric loss tangent >)

The resin sheets obtained in each example and each comparative example were thermally cured at 200℃for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces having a width of 2mm and a length of 80mm, and dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8GHz by the cavity method using a cavity perturbation method dielectric constant measuring device "CP521" manufactured by kanto applied electronics development company, and "Network Analyzer" E8362B "manufactured by agilent technology (Agilent Technologies). The measurement was performed on 2 test pieces, and an average value was calculated.

TABLE 1

In the table, "(a) content (mass%) means the content of the component (a) when the total content of the component (a) and the component (C) is 100 parts by mass, and" (D) content (mass%) means the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass.

In examples 1 to 6, it was confirmed that the same results as in the above examples were obtained even though the degree of the difference was found in the case where the components (C) to (G) were not contained.

Claims

1. A resin composition comprising:

(A) An aromatic hydrocarbon resin which contains aromatic rings as single rings or condensed rings and has 2 or more groups containing an oxygen atom bonded to the aromatic ring with respect to one of the aromatic rings;

(B) An active ester-based solidifying agent;

(C) An epoxy resin; and

(D) An inorganic filler material, a filler material,

wherein the component (C) does not include a substance belonging to the component (A),

(A) The component (C) is represented by the following formula (3),

in the above-mentioned formula (3),

OR ³¹ each independently represents the group containing an oxygen atom bonded to an aromatic ring;

R ³² each independently represents a 2-valent hydrocarbon group as an aromatic hydrocarbon group, or a 2-valent hydrocarbon group formed by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group;

n3 represents an integer of 1 to 10,

(A) The group containing an oxygen atom bonded to an aromatic ring in the component is an alkylene oxide group, an alkoxy group, or a hydroxyl group,

the dielectric loss tangent of a cured product obtained by thermally curing the resin composition at 200 ℃ for 90 minutes is 0.01 or less.

2. The resin composition according to claim 1, wherein the component (A) is represented by the following formula (4),

In formula (4), OR ⁴¹ Each independently represents the group containing an oxygen atom bonded to an aromatic ring, R ⁴² Each independently represents an alkylene group, and n4 represents an integer of 1 to 10.

3. The resin composition according to claim 1, wherein the component (A) is represented by the following formula (5),

in formula (5), OR ⁵¹ Each independently represents the group containing an oxygen atom bonded to an aromatic ring, R ⁵² Each independently represents an alkylene group, and n5 represents an integer of 1 to 10.

4. The resin composition according to claim 1, wherein the component (A) is represented by the following formula (6),

in formula (6), OR ⁶¹ Each independently represents the group containing an oxygen atom bonded to an aromatic ring, and n6 represents an integer of 1 to 10.

5. The resin composition according to claim 1, wherein the content of the component (C) is 1% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

6. The resin composition according to claim 1, wherein the content of the component (C) is 5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

7. The resin composition according to claim 1, wherein the content of the component (C) is 30% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

8. The resin composition according to claim 1, wherein the content of the component (C) is 20% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

9. The resin composition according to claim 1, wherein the content of the component (A) is 2 to 50 mass% based on 100 mass% of the total content of the component (A) and the component (C).

10. The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass or more, based on 100% by mass of the total content of the component (A) and the component (C).

11. The resin composition according to claim 1, wherein the content of the component (A) is 30% by mass or less, based on 100% by mass of the total content of the component (A) and the component (C).

12. The resin composition according to claim 1, wherein the content of the component (A) is 0.5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

13. The resin composition according to claim 1, wherein the content of the component (A) is 1% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

14. The resin composition according to claim 1, wherein the content of the component (A) is 15% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

15. The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

16. The resin composition according to claim 1, wherein the content of the component (B) is 1 to 30 mass% based on 100 mass% of the nonvolatile component in the resin composition.

17. The resin composition according to claim 1, wherein the content of the component (B) is 5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

18. The resin composition according to claim 1, wherein the content of the component (B) is 15% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

19. The resin composition according to claim 1, wherein the content of the component (D) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

20. The resin composition according to claim 1, wherein the content of the component (D) is 65% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

21. The resin composition according to claim 1, wherein the content of the component (D) is 90% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.

22. The resin composition according to claim 1, wherein the content of the component (D) is 80% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

23. The resin composition according to claim 1, which is a resin composition for forming an insulating layer of a multilayer printed wiring board.

24. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through hole with a top diameter of 70 μm or less.

25. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through hole with a top diameter of 35 μm or less.

26. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through hole with a top diameter of 10 μm or more.

27. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through-hole with a thickness-to-top diameter ratio of 0.5 or more,

the thickness to diameter ratio is the thickness/top diameter of the insulating layer, and the thickness and top diameter are in μm.

28. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through-hole with a thickness-to-top diameter ratio of 0.7 or more,

29. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through-hole with a thickness-to-top diameter ratio of 3 or less,

30. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a through-hole with a thickness-to-top diameter ratio of 1 or less,

31. A resin sheet, comprising:

support body

A resin composition layer comprising the resin composition according to any one of claims 1 to 30 provided on the support.

32. The resin sheet according to claim 31, wherein the thickness of the resin composition layer is 40 μm or less.

33. The resin sheet according to claim 31, wherein the thickness of the resin composition layer is 20 μm or less.

34. The resin sheet according to claim 31, wherein the thickness of the resin composition layer is 3 μm or more.

35. The resin sheet according to claim 31, wherein the thickness of the resin composition layer is 7 μm or more.

36. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 30.

37. A semiconductor device comprising the printed wiring board of claim 36.